WO2017029978A1 - 燃料電池用光硬化性シール剤、燃料電池およびシール方法 - Google Patents

燃料電池用光硬化性シール剤、燃料電池およびシール方法 Download PDF

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WO2017029978A1
WO2017029978A1 PCT/JP2016/072551 JP2016072551W WO2017029978A1 WO 2017029978 A1 WO2017029978 A1 WO 2017029978A1 JP 2016072551 W JP2016072551 W JP 2016072551W WO 2017029978 A1 WO2017029978 A1 WO 2017029978A1
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Prior art keywords
fuel cell
methacrylate
sealant
photocurable
component
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PCT/JP2016/072551
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English (en)
French (fr)
Japanese (ja)
Inventor
哲徳 曽我
麻央 穴井
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株式会社スリーボンド
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Priority to JP2017535320A priority Critical patent/JP6828230B2/ja
Priority to US15/752,494 priority patent/US20180241056A1/en
Priority to CA2995835A priority patent/CA2995835C/en
Priority to KR1020187005652A priority patent/KR102604161B1/ko
Priority to CN201680048479.3A priority patent/CN107925098B/zh
Priority to EP16836969.2A priority patent/EP3340352B1/en
Publication of WO2017029978A1 publication Critical patent/WO2017029978A1/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/028—Sealing means characterised by their material
    • H01M8/0284—Organic resins; Organic polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/08—Butenes
    • C08F10/10—Isobutene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/08—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms
    • C08F255/10—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms on to butene polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • C08F290/042—Polymers of hydrocarbons as defined in group C08F10/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9008—Organic or organo-metallic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/0273—Sealing or supporting means around electrodes, matrices or membranes with sealing or supporting means in the form of a frame
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/0286—Processes for forming seals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/30—Chemical modification of a polymer leading to the formation or introduction of aliphatic or alicyclic unsaturated groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/40—Chemical modification of a polymer taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8684—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8689—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02B90/10—Applications of fuel cells in buildings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a photocurable sealant for a fuel cell that is rapidly cured by irradiation with active energy rays such as ultraviolet rays and has excellent adhesion to an electrolyte membrane, PP, and PEN that are difficult to adhere.
  • a fuel cell is a power generator that extracts electricity by chemically reacting hydrogen and oxygen.
  • a fuel cell is a clean next-generation power generation device because it has high energy efficiency during power generation and water is generated by the reaction of hydrogen and oxygen.
  • fuel cells There are four types of fuel cells: solid polymer fuel cells, phosphoric acid fuel cells, molten carbonate fuel cells, and solid oxide fuel cells.
  • solid polymer fuel cells have an operating temperature. Since it has a relatively low temperature (around 80 ° C.) and high power generation efficiency, it is expected to be used in applications such as a power source for automobiles, a household power generator, a small power source for electronic devices such as a mobile phone, and an emergency power source.
  • the cell 1 of the polymer electrolyte fuel cell is an electrolyte membrane electrode assembly 5 (MEA) having a structure in which a polymer electrolyte membrane 4 is sandwiched between an air electrode 3a and a fuel electrode 3b. ), A frame 6 that supports the MEA, and a separator 2 in which a gas flow path is formed.
  • MEA electrolyte membrane electrode assembly 5
  • Patent Documents 5 and 6 disclose a photocurable sealant containing polyisobutylene diacrylate, a (meth) acryl monomer, and a photoinitiator.
  • the photocurable resin composition disclosed in Patent Documents 5 and 6 contains polyisobutylene diacrylate as a main component in order to obtain sealing properties, the photocurability is insufficient. Moreover, due to the low polarity of polyisobutylene diacrylate, there was a problem that the adhesion to various members was poor. Further, PP (polypropylene) and PEN (polyethylene naphthalate), which are typical materials for polymer electrolyte membranes and frames of fuel cells, are hard-to-adhere members, and the photocurable resin compositions of Patent Documents 5 and 6 Then, it was difficult to bond.
  • a photocurable sealant for a fuel cell that can be quickly cured by irradiation with active energy rays such as ultraviolet rays and has an adhesive force to electrolyte membranes, PP, and PEN, which are difficult-to-adhere materials.
  • the present invention has been made in view of the above situation, and is a fuel cell that is rapidly cured by irradiation with active energy rays such as ultraviolet rays and has excellent adhesion to electrolyte membranes, PP, and PEN, which are difficult-to-adhere materials.
  • An object of the present invention is to provide a photocurable sealant for use.
  • the present invention is a photocurable sealant for fuel cells, comprising the following components (A) to (C).
  • C) component methacrylate monomer.
  • a photocurable sealant for a fuel cell comprising the following components (A) to (C): Component (A): Polyisobutylene polymer having one or more (meth) acryloyl groups in the molecule and having a polyisobutylene skeleton containing a — [CH 2 C (CH 3 ) 2 ] — unit (B) component: initiation of radical photopolymerization Agent (C) Component: Methacrylate Monomer [2] The photocurability for a fuel cell according to the above [1], wherein the component (C) is a methacrylate monomer having an alkyl group having 5 to 30 carbon atoms or a methacrylate monomer having an alicyclic group having 5 to 30 carbon atoms. Sealing agent.
  • the component (C) is a methacrylate monomer having an alkyl group having 5 to 30 carbon atoms, and the methacrylate monomer having an alkyl group is heptyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, isooctyl methacrylate, decyl methacrylate, dodecyl methacrylate.
  • the component (C) is a methacrylate monomer having an alicyclic group having 5 to 30 carbon atoms, and the methacrylate monomer having the alicyclic group is cyclohexyl methacrylate, 4-butylcyclohexyl methacrylate, dicyclopentanyl methacrylate,
  • Photo-curable sealant [4] The light for a fuel cell according to any one of [1] to [3], wherein the compounding amount of the component (C) is 3 to 300 parts by mass with respect to 100 parts by mass of the component (A). Curable sealant. [5] The photocurable sealant for a fuel cell according to any one of [1] to [4], wherein the component (A) is a polyisobutylene polymer represented by the general formula (1). (R 1 represents a monovalent or polyvalent aromatic hydrocarbon group, or a monovalent or polyvalent aliphatic hydrocarbon group, and PIB represents the above-mentioned poly (CH 2 C (CH 3 ) 2 ] — unit).
  • R 4 represents an isobutylene skeleton, and R 4 represents a divalent hydrocarbon group which may contain an oxygen atom having 2 to 6 carbon atoms, R 2 and R 3 each independently represent a hydrogen atom, a monovalent having 1 to 20 carbon atoms.
  • R 5 represents a hydrogen atom, a methyl group, an ethyl group or a propyl group, and n is an integer of 1 to 6.
  • the photocurable sealant for a fuel cell is a sealant around any member of the group consisting of a separator, a frame, an electrolyte, a fuel electrode, an air electrode, and an electrolyte membrane electrode assembly, which are members in a fuel cell.
  • the photocurable sealant for a fuel cell according to any one of the above [1] to [5].
  • the photocurable sealant for a fuel cell is a sealant between adjacent separators in a fuel cell, a sealant between a separator and a frame in a fuel cell, or a frame and an electrolyte membrane or an electrolyte membrane electrode of a fuel cell
  • a method of sealing at least a portion between at least two flanges of a part to be sealed having at least two flanges, wherein at least one of the flanges is capable of transmitting light of active energy rays The step of applying the photocurable sealant for fuel cells according to any one of [1] to [5] on one surface, one flange applied with the photocurable resin composition, and the other Attaching the flange to the fuel cell photocurable sealant, and irradiating an active energy ray through the light transmissive flange to cure the fuel cell photocurable sealant, Sealing at least part of the gap between the two flanges.
  • a method for sealing at least a part between at least two flanges of a part to be sealed having at least two flanges, wherein at least one of the flanges is provided with any one of the above [1] to [5] Applying the photocurable sealant for a fuel cell according to the item, irradiating the applied photocurable sealant for a fuel cell with active energy rays to cure the photocurable sealant for a fuel cell, A step of forming a gasket comprising a cured product of a photocurable resin composition, the other flange is disposed on the gasket, and the one flange coated with the photocurable resin composition and the other flange are connected to the gasket; And sealing at least a part between the at least two flanges.
  • a method for sealing at least a portion between at least two flanges of a part to be sealed having at least two flanges, the step of disposing a gasket forming mold on at least one of the flanges, the gasket The step of injecting the photocurable sealant for a fuel cell according to any one of [1] to [5] above into at least a part of a gap between a forming mold and a flange on which the mold is disposed. Irradiating the photocurable sealant for fuel cells with the active energy ray to cure the photocurable sealant for fuel cells to form a gasket made of a cured product of the photocurable sealant for fuel cells.
  • the sealing method characterized by crimping through the gasket, comprising the step, of sealing at least a portion between the at least two flanges.
  • the present invention has been made in view of the above situation, and is a fuel cell that is rapidly cured by irradiation with active energy rays such as ultraviolet rays and has excellent adhesion to electrolyte membranes, PP, and PEN, which are difficult-to-adhere materials.
  • active energy rays such as ultraviolet rays
  • the photocurable sealing agent for use is provided.
  • the component (A) used in the present invention may be a polyisobutylene polymer having a polyisobutylene skeleton containing a — [CH 2 C (CH 3 ) 2 ] — unit having at least one (meth) acryloyl group in the molecule.
  • the component (A) may have, for example, a — [CH 2 C (CH 3 ) 2 ] — unit (polyisobutylene skeleton), and other than “— [CH 2 C (CH 3 ) 2 ] — units”. It may be a polyisobutylene polymer containing the “constituent unit”.
  • the component (A) contains — [CH 2 C (CH 3 ) 2 ] — units, for example, 70% by mass or more, preferably 75% by mass or more, more preferably 80% by mass or more, relative to the total amount of the structural units. It is appropriate to include.
  • the component (A) includes — [CH 2 C (CH 3 ) 2 ] — units, for example, 100% by mass or less, in another aspect, 95% by mass or less, and in another aspect, 90% by mass or less. Is appropriate.
  • the component (A) preferably has 1 to 6 (meth) acryloyl groups, more preferably 2 to 4, more preferably 2 to 3, and particularly preferably 2 (meth) acryloyl groups.
  • the polymer is not limited by theory, but can be defined as, for example, a compound having a repeating unit of a monomer in the main chain of the polymer and comprising 100 or more repeating units.
  • the component (A) is preferably a polymer having a polyisobutylene skeleton represented by the general formula (1) from the viewpoint of excellent photocurability and adhesion to an electrolyte membrane.
  • Specific examples of the component (A) include polyisobutylene polymers having a (meth) acryloyloxyalkoxyphenyl group.
  • the main skeleton of the component (A) in the present invention is a polyisobutylene skeleton, but as the monomer constituting the polyisobutylene skeleton, other than the main use of isobutylene, there is no limitation as long as the effects of the present invention are not impaired. These monomers may be copolymerized.
  • (A) component is excellent in workability
  • R 1 represents a monovalent or polyvalent aromatic hydrocarbon group or a monovalent or polyvalent aliphatic hydrocarbon group, preferably a polyvalent aromatic hydrocarbon group, particularly preferably.
  • PIB is the - [CH 2 C (CH 3 ) 2] - comprising units (or - [CH 2 C (CH 3 ) 2] - comprising units) - [CH 2 C (CH 3) 2] - units
  • the polyisobutylene skeleton containing is shown.
  • R 4 represents a divalent hydrocarbon group having 2 to 6 carbon atoms which may contain an oxygen atom, preferably a hydrocarbon group having 2 or 3 carbon atoms.
  • R 2 and R 3 each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrogen atom.
  • R 5 represents a hydrogen atom, a methyl group or an ethyl group, preferably a hydrogen atom or a methyl group.
  • n is an integer of 1 to 6, particularly preferably an integer of 2 to 4.
  • the molecular weight of the component (A) in the present invention is not particularly limited, but the number average molecular weight is preferably, for example, from 500 to 500,000, more preferably from the viewpoint of fluidity and physical properties after curing. 000 to 100,000, particularly preferably 3,000 to 50,000.
  • the number average molecular weight was calculated by a standard polystyrene conversion method using size permeation chromatography (SEC).
  • SEC size permeation chromatography
  • the viscosity at 25 ° C. of the component (A) in the present invention is not particularly limited, but it is preferably, for example, 5 to 3000 Pa ⁇ s, more preferably 50 to 2500 Pa ⁇ s from the viewpoint of workability and the like. Preferably, it is 100 to 2000 Pa ⁇ s.
  • the viscosity is, for example, 5 Pa ⁇ s or more, preferably 50 Pa ⁇ s or more, more preferably 100 Pa ⁇ s or more, for example, 3000 Pa ⁇ s or less, preferably 2500 Pa ⁇ s or less, more preferably 2000 Pa ⁇ s or less. It is. A particularly preferred viscosity is 1550 Pa ⁇ s. Unless otherwise specified, the viscosity was measured at 25 ° C. using a cone plate viscometer.
  • the viscosity at 25 ° C. of the component (A) in the present invention is not particularly limited, but it is preferably, for example, 5 to 3000 Pa ⁇ s, more preferably 50 to 2500 Pa ⁇ s from the viewpoint of workability and the like. Preferably, it is 100 to 2000 Pa ⁇ s.
  • the viscosity is, for example, 5 Pa ⁇ s or more, preferably 50 Pa ⁇ s or more, more preferably 100 Pa ⁇ s or more, for example, 3000 Pa ⁇ s or less, preferably 2500 Pa ⁇ s or less, more preferably 2000 Pa ⁇ s or less. It is.
  • a particularly preferred viscosity is 1550 Pa ⁇ s. Unless otherwise specified, the viscosity was measured at 25 ° C. using a cone plate viscometer.
  • a well-known method can be used. For example, Polymer Bulletin, Vol. 6, pages 135 to 141 (1981), T.M. P. Liao and J.A. P. Kennedy and Polymer Bulletin, Vol. 20, pages 253-260 (1988), Puskas et al. And a method obtained by reacting the terminal hydroxyl group polyisobutylene polymer disclosed in (1) with acryloyl chloride or methacryloyl chloride.
  • a method obtained by reaction a method obtained by reacting a terminal hydroxyl group polyisobutylene polymer, a (meth) acryloyl group and a compound having an isocyanate group, or a compound having a terminal hydroxyl group polyisobutylene polymer and an isocyanate group
  • the production method of the polyisobutylene polymer represented by the general formula (1) is not particularly limited, but preferably, the halogen-terminated polyisobutylene polymer disclosed in JP2013-216682A and the general formula ( Examples thereof include a method obtained by reacting a compound having a (meth) acryloyl group and a phenoxy group as represented by 2).
  • the halogen-terminated polyisobutylene polymer can be obtained by a known method, for example, by cationic polymerization, and more preferably by living cationic polymerization.
  • R 2, R 3 , R 4 , and R 5 may be as defined in formula (1) above.
  • R 4 represents a divalent hydrocarbon group that may contain an oxygen atom having 2 to 6 carbon atoms.
  • R 2 and R 3 each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.
  • R 5 represents a hydrogen atom, a methyl group, or an ethyl group. Examples of the compound represented by the above formula (2) include phenoxymethyl acrylate, phenoxyethyl acrylate, and phenoxypropyl acrylate, and phenoxyethyl acrylate is preferable.
  • the radical photopolymerization initiator that is the component (B) used in the present invention is limited as long as it is a compound that generates a radical or the like that cures the component (A) of the present invention by irradiating active energy rays. is not.
  • the active energy ray is a broad sense such as radiation such as ⁇ ray or ⁇ ray, electromagnetic wave such as ⁇ ray or X ray, electron beam (EB), ultraviolet ray of about 100 to 400 nm, visible ray of about 400 to 800 nm, or the like. It contains all light, preferably ultraviolet light.
  • Examples of the component (B) include an acetophenone photoradical polymerization initiator, a benzoin photoradical polymerization initiator, a benzophenone photoradical polymerization initiator, a thioxanthone photoradical polymerization initiator, and an acylphosphine oxide photoradical polymerization initiator. , Titanocene photoradical polymerization initiators, etc. Among them, acetophenone photoradical polymerization initiator, benzophenone photoradical polymerization initiation from the viewpoint of obtaining a cured product excellent in curability by irradiation with active energy rays An acylphosphine oxide-based photoradical polymerization initiator is preferred. Moreover, these may be used independently and 2 or more types may be used together.
  • the acetophenone photoradical polymerization initiator is not particularly limited, and examples thereof include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy ) Phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2- Examples include, but are not limited to, dimethylamino-1- (4-morpholinophenyl) butanone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer.
  • acetophenone photoradical polymerization initiators examples include IRGACURE 184, IRGACUR 1173, IRGACURE 2959, IRGACURE 127 (manufactured by BASF), and ESACURE KIP-150 (manufactured by Lamberti spa).
  • benzophenone photoradical polymerization initiator examples include benzophenone, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 2-methylbenzophenone, 2-ethylbenzophenone, 3-methylbenzophenone, 3-ethylbenzophenone, 4-methylbenzophenone.
  • the acylphosphine oxide photo radical polymerization initiator is not particularly limited, and examples thereof include bis (2,4,6-trimethylbenzoyl) -phenyl-phosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phos. Examples include, but are not limited to, fin oxide. Examples of commercially available acylphosphine oxide photoradical polymerization initiators include IRGACURE TPO, IRGACURE819, IRGACURE819DW (manufactured by BASF).
  • the blending amount of the component (B) of the present invention is not particularly limited, but is preferably 0.1 to 30 parts by weight, more preferably 100 parts by weight with respect to 100 parts by weight of the component (A).
  • the amount is 0.5 to 20 parts by mass, and particularly preferably 1 to 15 parts by mass.
  • the methacrylate monomer which is the component (C) of the present invention is a compound which is polymerized by the radical species generated by the component (B) of the present invention, and the component (C) of the present invention is selected from various reactive diluents.
  • Component (C) is a methacrylate monomer having an alkyl group having 5 to 30 carbon atoms or an alicyclic group having 5 to 30 carbon atoms because it is compatible with the component (A) of the present invention and has excellent photocurability.
  • a methacrylate monomer having an alicyclic group is particularly preferable.
  • said carbon number it is 2 or more, for example, Preferably it is 3 or more, More preferably, it is 5 or more, More preferably, it is 7 or more, for example, 30 or less, Preferably it is 20 or less, More preferably, it is 15 or less. Preferably it is 10 or less.
  • (C) component excludes (A) component of this invention.
  • the methacrylate monomer having an alkyl group having 5 to 30 carbon atoms is not particularly limited.
  • methacrylate monomer having an alicyclic group having 5 to 30 carbon atoms examples include cyclohexyl methacrylate, 4-butylcyclohexyl methacrylate, dicyclopentanyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxy methacrylate, and isobornyl methacrylate.
  • Adamantyl methacrylate, dicyclopentenyl dimethacrylate, tricyclodecane dimethanol dimethacrylate and the like, and the component (C) can be used alone or as a mixture of two or more.
  • Examples of commercially available methacrylate monomers having an alkyl group having 5 to 30 carbon atoms include SMA (manufactured by Mitsubishi Gas Chemical Company), LMA, SMA (manufactured by BASF), light ester EH, light ester ID, and light ester L. , Light ester L-7, light ester S (Kyoeisha Chemical Co., Ltd.), S (manufactured by Shin-Nakamura Chemical Co., Ltd.), LMA, SMA, HMA (manufactured by Arkema), LMA, SMA (manufactured by Mitsubishi Rayon Co., Ltd.), SR242 SR313, SR324, SR493D (manufactured by Sartomer), and the like.
  • methacrylate monomers having an alicyclic group having 5 to 30 carbon atoms include FA-512M, FA-512MT, FA-513M (manufactured by Hitachi Chemical Co., Ltd.), DCP (Shin Nakamura Chemical Co., Ltd.). Manufactured), CHMA (manufactured by BASF), BX-ADMA, BX-DCPMA (manufactured by Bimax), light ester IB-X (manufactured by Kyoeisha Chemical Co., Ltd.), CHMA (manufactured by Mitsubishi Rayon), SR423 (manufactured by Sartomer) Etc.
  • the amount of component (C) is not particularly limited, but is preferably 3 to 300 parts by weight, more preferably 5 to 200 parts by weight, and particularly preferably 10 to 10 parts by weight with respect to 100 parts by weight of component (A). 100 parts by mass. In this case, if the component (C) is 3 parts by mass or more, the surface curability is not lowered, and if it is 300 parts by mass or less, the moisture permeability of the cured product of the photocurable sealant is lowered. This is preferable.
  • an acrylate monomer an oligomer having a (meth) acryloyl group (not including the components (A) and (C) of the present invention), thermal radical initiation, as long as the object of the present invention is not impaired.
  • Agents polythiol compounds, tertiary amine compounds, various elastomers such as styrene copolymers, fillers, storage stabilizers, antioxidants, light stabilizers, plasticizers, pigments, flame retardants, adhesion promoters, and surfactants Additives such as agents can be used.
  • the acrylate monomer is not particularly limited.
  • the oligomer having the (meth) acryloyl group (not including the components (A) and (C) of the present invention) is not particularly limited.
  • urethane (meth) acrylate having a polybutadiene skeleton hydrogenated polybutadiene skeleton Urethane (meth) acrylate, Urethane (meth) acrylate with polycarbonate skeleton, Urethane (meth) acrylate with polyether skeleton, Urethane (meth) acrylate with polyester skeleton, Urethane (meth) acrylate with castor oil skeleton, Isoprene (meth) acrylate
  • Examples include hydrogenated isoprene-based (meth) acrylate, epoxy (meth) acrylate, (meth) acrylic group-containing acrylic polymer, and among others, because of excellent compatibility with the components (A) and (C) of the present invention, Polybutadiene skeleton Down (meth) acrylate,
  • the thermal radical initiator is not particularly limited, and examples thereof include ketone peroxide, peroxyketal, dialkyl peroxide, hydroperoxide, peroxyester, diacyl peroxide, and peroxydicarbonate. These compounds may be used alone or in combination of two or more.
  • polythiol compound examples include, but are not limited to, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), Trimethylol ethane tris (3-mercaptobutyrate), trimethylol ethane tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoglycolate), butanediol bis (3-mercaptoglycolate), trimethylolpropane tris (3-mercaptoglycolate), pentaerythritol tetrakis (3-mercaptoglycolate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, penta Lithritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-
  • polythiol compounds examples include TMTP, PETP (manufactured by Sakai Chemical Co., Ltd.), TEMPIC, TMMP, PEMP, PEMP-II-20P, DPMP (manufactured by SC Organic Chemical Co., Ltd.), MTNR1, MTBD1, MTPE1 (Showa) But not limited to these. These compounds may be used alone or in combination of two or more.
  • a tertiary amine compound may be blended.
  • the tertiary amine compound is not particularly limited.
  • a styrene copolymer may be blended for the purpose of adjusting the rubber physical properties of the cured product.
  • the styrene copolymer is not particularly limited.
  • styrene-butadiene copolymer styrene-isoprene copolymer (SIP), styrene-butadiene copolymer (SB), styrene-ethylene-butylene-styrene copolymer.
  • SEBS polymer
  • SIBS styrene-isobutylene-styrene copolymer
  • AS acrylonitrile-styrene copolymer
  • ABS styrene-butadiene-acrylonitrile copolymer
  • a filler that does not impair storage stability may be added to the present invention.
  • specific examples include organic powders, inorganic powders, and metallic powders.
  • the inorganic powder filler include glass, fumed silica, alumina, mica, ceramics, silicone rubber powder, calcium carbonate, aluminum nitride, carbon powder, kaolin clay, dry clay mineral, and dry diatomaceous earth.
  • the blending amount of the inorganic powder is preferably about 0.1 to 100 parts by mass with respect to 100 parts by mass of the component (A). If it is 0.1 parts by mass or more, a sufficient effect can be expected, and if it is 100 parts by mass or less, the fluidity as a photocurable sealant can be sufficiently maintained and a certain workability can be maintained, which is preferable.
  • Fumed silica can be blended for the purpose of adjusting the viscosity of the photocurable sealant for fuel cells or improving the mechanical strength of the cured product.
  • those hydrophobized with organochlorosilanes, polyorganosiloxane, hexamethyldisilazane, etc. can be used.
  • Specific examples of fumed silica include commercial products such as Aerosil R974, R972, R972V, R972CF, R805, R812, R812S, R816, R8200, RY200, RX200, RY200S, R202 manufactured by Nippon Aerosil. .
  • Examples of the organic powder filler include polyethylene, polypropylene, nylon, crosslinked acrylic, crosslinked polystyrene, polyester, polyvinyl alcohol, polyvinyl butyral, and polycarbonate.
  • the blending amount of the organic powder is preferably about 0.1 to 100 parts by mass with respect to 100 parts by mass of the component (A). If it is 0.1 parts by mass or more, a sufficient effect can be expected, and if it is 100 parts by mass or less, the fluidity of the photocurable sealing agent can be sufficiently maintained and workability can be maintained, which is preferable.
  • Examples of the filler for the metallic powder include gold, platinum, silver, copper, indium, palladium, nickel, alumina, tin, iron, aluminum, and stainless steel.
  • the blending amount of the metallic powder is preferably about 0.1 to 100 parts by mass, more preferably 1 to 50 parts by mass with respect to 100 parts by mass of the component (A).
  • a storage stabilizer may be added to the present invention.
  • a radical absorbent such as benzoquinone, hydroquinone, hydroquinone monomethyl ether, a metal chelating agent such as ethylenediaminetetraacetic acid or its 2-sodium salt, oxalic acid, acetylacetone, o-aminophenol, etc. may be added. it can.
  • An antioxidant may be added to the present invention.
  • the antioxidant include ⁇ -naphthoquinone, 2-methoxy-1,4-naphthoquinone, methyl hydroquinone, hydroquinone, hydroquinone monomethyl ether, mono-tert-butyl hydroquinone, 2,5-di-tert-butyl hydroquinone, p Quinone compounds such as benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-di-tert-butyl-p-benzoquinone; phenothiazine, 2,2-methylene-bis (4-methyl-6-tert- Butylphenol), catechol, tert-butylcatechol, 2-butyl-4-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, 2-tert-butyl-6- (3-tert-butyl-2- Hydroxy-5-methylbenzyl) -4-methyl Phenyl acrylate
  • a light stabilizer may be added to the present invention.
  • the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, and 4-benzoyl.
  • An adhesion-imparting agent may be added to the present invention.
  • adhesion promoter 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane , Methacryloxyoctyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris ( ⁇ -methoxyethoxy) silane, ⁇ -chloropropyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -amino
  • hydroxyethyl methacrylate phosphate, methacryloxyoxyethyl acid phosphate, methacryloxyoxyethyl acid phosphate monoethylamine half salt, 2-hydroxyethyl methacrylate phosphate and the like are preferable.
  • the content of the adhesion-imparting agent is preferably 0.05 to 30 parts by mass, more preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the component (A).
  • the photocurable sealant for fuel cells of the present invention can be produced by a conventionally known method.
  • a predetermined amount of components (A) to (C) and other optional components are blended, and using a mixing means such as a mixer, the temperature is preferably 10 to 70 ° C., more preferably 20 to 50 ° C.
  • a mixing means such as a mixer
  • the temperature is preferably 10 to 70 ° C., more preferably 20 to 50 ° C.
  • it can be produced by mixing at normal temperature (25 ° C.), preferably 0.1 to 5 hours, more preferably 30 minutes to 3 hours, particularly preferably about 60 minutes.
  • ⁇ Application method> As a method for applying the photocurable sealant for fuel cells of the present invention to an adherend, known sealants and adhesive methods are used. For example, methods such as dispensing, spraying, inkjet, screen printing, gravure printing, dipping, spin coating using an automatic coater can be used.
  • the photocurable sealing agent for fuel cells of this invention is a liquid at 25 degreeC from a viewpoint of applicability
  • the light source for curing the photocurable sealant for fuel cells of the present invention by irradiating the active energy rays as described above, for example, light such as ultraviolet rays and visible light, is not particularly limited. Examples thereof include a pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a black light lamp, a microwave excitation mercury lamp, a metal halide lamp, a sodium lamp, a halogen lamp, a xenon lamp, an LED, a fluorescent lamp, sunlight, and an electron beam irradiation device.
  • the irradiation amount of light irradiation is preferably 10 kJ / m 2 or more, more preferably 15 kJ / m 2 or more, from the viewpoint of the properties of the cured product.
  • the cured product of the present invention is formed by irradiating the photocurable resin composition of the present invention with active energy rays such as ultraviolet rays by the above curing method.
  • active energy rays such as ultraviolet rays
  • any curing method may be used.
  • the photocurable sealant of the present invention or a cured product thereof is a rubber elastic body excellent in low gas permeability, low moisture permeability, heat resistance, acid resistance, and flexibility. Therefore, fuel cell, solar cell, dye-sensitized solar cell, lithium ion battery, electrolytic capacitor, liquid crystal display, organic EL display, electronic paper, LED, hard disk device, photodiode, optical communication / circuit, electric wire, Examples include laminates such as cables / optical fibers, optical isolators, IC cards, sensors, substrates, pharmaceutical / medical instruments / devices, and the like.
  • the photocurable sealing agent of the present invention is rapidly cured by irradiation with active energy rays such as ultraviolet rays, and has excellent adhesion to an electrolyte membrane that is a difficult-to-adhere material. Use is particularly preferred.
  • a fuel cell is a power generator that extracts electricity by chemically reacting hydrogen and oxygen.
  • fuel cells there are four types of fuel cells: solid polymer fuel cells, phosphoric acid fuel cells, molten carbonate fuel cells, and solid oxide fuel cells. Since the operating temperature is relatively low (around 80 ° C.) and high power generation efficiency, it is used for applications such as automobile power sources, household power generators, small power supplies for electronic devices such as mobile phones, and emergency power supplies.
  • a cell 1 of a typical polymer electrolyte fuel cell is an electrolyte membrane electrode assembly having a structure in which a polymer electrolyte membrane 4 is sandwiched between an air electrode 3a and a fuel electrode 3b. 5 (MEA), a frame 6 that supports the MEA, and a separator 2 in which a gas flow path is formed.
  • fuel gas hydrogen gas
  • oxidizing gas oxygen gas
  • the cooling water flows through the cooling water passage 9 for the purpose of relaxing the heat generation during power generation.
  • a package in which several hundreds of cells are stacked is called a cell stack 10 as shown in FIG.
  • a sealing agent is frequently used for the purpose of preventing leakage of fuel gas, oxygen gas and the like. Specifically, a sealant is used between adjacent separators, between the separator and the frame, between the frame and the electrolyte membrane or MEA, and the like.
  • the polymer electrolyte membrane examples include a cation exchange membrane having ion conductivity, preferably a chemically stable and strong operation at a high temperature, and examples thereof include a fluorine polymer having a sulfonic acid group. It is done.
  • examples of commercially available products include Nafion (registered trademark) manufactured by DuPont, Flemion (registered trademark) manufactured by Asahi Kasei Corporation, and Aciplex (registered trademark) manufactured by Asahi Glass Co., Ltd.
  • the polymer electrolyte membrane is a material that hardly adheres, but can be adhered by using the photocurable sealant for fuel cells of the present invention. Nafion (registered trademark)
  • the fuel electrode is called a hydrogen electrode or an anode, and a known one is used.
  • carbon in which a catalyst such as platinum, nickel, ruthenium or the like is supported is used.
  • the air electrode is called an oxygen electrode or a cathode, and a known one is used.
  • carbon in which a catalyst such as platinum or an alloy is supported is used.
  • the surface of each electrode may be provided with a gas diffusion layer that functions to diffuse the gas and keep the electrolyte moist.
  • a known gas diffusion layer is used, and examples thereof include carbon paper, carbon cloth, and carbon fiber.
  • the separator 2 has a fine flow path with irregularities, through which fuel gas and oxidizing gas pass and are supplied to the electrodes.
  • the separator is made of aluminum, stainless steel, titanium, graphite, carbon, or the like.
  • the frame is used to support and reinforce a thin electrolyte membrane or MEA so as not to be broken.
  • the material of the frame include thermoplastic resins such as polyvinyl chloride, polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polypropylene (PP), and polycarbonate.
  • thermoplastic resins such as polyvinyl chloride, polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polypropylene (PP), and polycarbonate.
  • PEN and PP are particularly preferable as the adhesion target of the present invention.
  • the fuel cell of the present invention is a fuel cell characterized by being sealed with the photocurable sealant for fuel cells of the present invention or a cured product thereof.
  • the member that needs to be sealed in the fuel cell include a separator, a frame, an electrolyte, a fuel electrode, an air electrode, and an MEA. More specific seal locations include between adjacent separators, between separators and frames, between frames and electrolyte membranes or MEAs, and the like.
  • the purpose of the main seal “between the separator and the frame” or “between the polymer electrolyte membrane or MEA and the frame” is to prevent gas mixing and leakage, and between the adjacent separators.
  • the purpose of the seal is to prevent gas leakage and to prevent cooling water from leaking from the cooling water flow path to the outside. In addition, since it becomes a strong acid atmosphere with the acid generated from the electrolyte membrane, the sealant is required to have acid resistance.
  • the sealing method using the photocurable sealant for fuel cells of the present invention is not particularly limited, but typically, FIPG (form in place gasket), CIPG (cure in place gasket), MIPG (mold in place) Gasket), liquid injection molding and the like.
  • FIPG means that the photocuring sealant for fuel cells of the present invention is applied to the flange of the part to be sealed with an automatic coating device or the like and bonded to the other flange to transmit light of active energy rays such as ultraviolet rays.
  • This is a technique of irradiating from a possible flange side, curing the photocurable sealant for fuel cells, and adhesively sealing. More specifically, it is a method for sealing at least a part between at least two flanges of a part to be sealed having at least two flanges, wherein at least one of the flanges can transmit light of active energy rays.
  • a step of applying the photocurable sealant for a fuel cell to at least one surface of the flange, the one flange and the other flange coated with the photocurable resin composition are connected to the light for the fuel cell.
  • CIPG is a photocuring sealant for fuel cells that is bead-coated on the flange of a part to be sealed by an automatic coating apparatus or the like and irradiated with active energy rays such as ultraviolet rays. Is cured to form a gasket. And it is the technique of pasting together and compressing and sealing with the other flange. More specifically, there is provided a method for sealing at least a part between at least two flanges of a part to be sealed having at least two flanges, wherein at least one of the flanges includes the above-described fuel cell light.
  • a mold In MIPG, a mold is pressed against a flange of a part to be sealed in advance, a photocurable sealant for a fuel cell is injected into a cavity formed between the mold of the light transmissive material and the flange, and an activity such as ultraviolet rays is applied. It is irradiated with energy rays and photocured to form a gasket. And it is the technique of pasting together and compressing and sealing with the other flange.
  • the mold is preferably made of a light transmissive material, and specific examples include glass, polymethyl methacrylate (PMMA), polycarbonate, cycloolefin polymer, and olefin.
  • a release agent such as a fluorine type or a silicone type in advance to the mold in order to facilitate removal from the mold after the gasket is formed. More specifically, a method for sealing at least a part between at least two flanges of a part to be sealed having at least two flanges, wherein a gasket forming mold is disposed on at least one of the flanges. A step of injecting the above-described photocurable sealant for a fuel cell into at least a part of a gap between the gasket-forming die and a flange on which the die is arranged, and the photocurable property for a fuel cell.
  • a release agent such as a fluorine type or a silicone type
  • a sealing method which comprises a step, to seal at least a portion between the at least two flanges.
  • Liquid injection molding means that the photocurable sealant for fuel cells of the present invention is poured into a metal mold capable of transmitting light at a specific pressure, and irradiated with active energy rays such as ultraviolet rays to be photocured to form a gasket. . And it is the technique of pasting together and compressing and sealing with the other flange.
  • the mold is preferably made of a light transmissive material, and specific examples include glass, PMMA, polycarbonate, cycloolefin polymer, and olefin.
  • a release agent such as a fluorine type or a silicone type in advance to the mold in order to facilitate removal from the mold after the gasket is formed.
  • the product was dissolved in 3000 ml of n-hexane, washed three times with 3000 ml of pure water, reprecipitated from methanol, and then the solvent was reduced in pressure.
  • the polyisobutylene polymer (a1) which has acryloyloxyethoxyphenyl group was obtained by distilling down and vacuum-drying the obtained polymer at 80 degreeC for 24 hours.
  • A1 contains a — [CH 2 C (CH 3 ) 2 ] — unit and contains two acryloyl groups. More specifically, a1 are the compounds of formula (1), R 1 represents a phenylene group, PIB represents a polyisobutylene backbone, R 4 represents a hydrocarbon group having 2 carbon atoms, R 2 and R 3 Each independently represents a hydrogen atom, R 5 represents a hydrogen atom, and n is a polyisobutylene polymer of 2.
  • the number average molecular weight of the a1 component (standard polystyrene conversion method using size permeation chromatography (SEC)) is 11,100, and the viscosity of the a1 component (viscosity at 25 ° C. using a cone plate viscometer). Measurement) was 1550 Pa ⁇ s.
  • Example 1 100 parts by mass of a polyisobutylene polymer (a1) having an acryloyloxyethoxyphenyl group as the component (A) of the present invention, and 2-hydroxy-2-methyl-1-phenyl-propan-1-one (IRGACURE 1173) as the component (B) 3 parts by weight of BASF), 50 parts by weight of dicyclopentanyl methacrylate (FA-513M, manufactured by Hitachi Chemical Co., Ltd.), and 3-methacryloxypropyltrimethoxysilane (KBM503, Shin-Etsu Chemical Co., Ltd.) as component (C) 3 parts by mass) were added and mixed with a planetary mixer for 60 minutes at room temperature under light shielding to obtain Example 1 which is a photocurable sealant for fuel cells. In addition, Example 1 was liquid at 25 degreeC.
  • Example 2 was obtained in the same manner as in Example 1 except that isobornyl methacrylate (SR-423, manufactured by Sartomer) was used in place of dicyclopentanyl methacrylate. In addition, Example 2 was liquid at 25 degreeC.
  • SR-423 isobornyl methacrylate
  • Example 3 was prepared in the same manner as in Example 1 except that stearyl methacrylate (SMA, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used instead of dicyclopentanyl methacrylate. In addition, Example 3 was liquid at 25 degreeC.
  • SMA stearyl methacrylate
  • Example 3 was liquid at 25 degreeC.
  • Example 4 was prepared in the same manner as in Example 1 except that 50 parts by mass of dicyclopentanyl methacrylate was changed to 100 parts by mass.
  • Example 4 was prepared in the same manner as in Example 1 except that 50 parts by mass of dicyclopentanyl methacrylate was changed to 20 parts by mass.
  • Comparative example 1 A comparative example 1 was prepared in the same manner as in Example 1 except that dicyclopentanyl acrylate (FA-513AS, manufactured by Hitachi Chemical Co., Ltd.) was used instead of dicyclopentanyl methacrylate. Obtained.
  • Comparative example 2 A comparative example 2 was obtained in the same manner as in Example 1, except that isobornyl acrylate (IBX-A, manufactured by Kyoeisha Chemical Co., Ltd.) was used instead of dicyclopentanyl methacrylate. It was.
  • IBX-A isobornyl acrylate
  • test methods used in the examples and comparative examples in Table 1 are as follows.
  • the test piece was bonded by 10 mm ⁇ length 2 mm, and cured by irradiating with ultraviolet rays for 20 seconds from the PP film so as to obtain an integrated light amount of 45 kJ / m 2 .
  • ⁇ Adhesion test for PEN> The photocurable sealant of Example 1 and Comparative Example 1 was applied to a 400 ⁇ m PP film so as to have a thickness of 50 ⁇ m, and PEN was bonded with a width of 10 mm ⁇ a length of 2 mm, and the integrated light amount was 45 kJ / m 2 from the PP film.
  • the test piece was cured by irradiating with ultraviolet rays for 20 seconds.
  • the cured product of the photocurable sealant for fuel cells is peeled from the electrolyte membrane together with the PP film in the direction of 180 degrees at a speed of 10 mm / min using a tensile tester. Evaluation was performed based on the following criteria.
  • Peel adhesion strength ⁇ (excellent): 0.2 N / mm or more ⁇ (good): 0.1 N / mm or more and less than 0.2 N / mm x (defect): less than 0.1 N / mm
  • Example 1 According to Examples 1 to 5 in Table 1, it can be seen that the present invention is rapidly cured by irradiation with active energy rays such as ultraviolet rays (20 seconds), and is excellent in adhesion to an electrolyte membrane that is a difficult-to-adhere material. . Moreover, according to Example 1, it turned out that the adhesiveness with respect to PEN is also excellent.
  • active energy rays such as ultraviolet rays (20 seconds
  • Comparative Examples 1 and 2 use dicyclopentanyl acrylate and isobornyl acrylate instead of the component (C) of the present invention. The result was inferior. Furthermore, according to the comparative example 1, it turns out that the adhesiveness with respect to PEN is inferior.
  • Comparative example 3 A comparative example 3 was obtained in the same manner as in Example 1, except that polybutadiene skeleton urethane dimethacrylate (TE-2000, manufactured by Nippon Soda Co., Ltd.) was used instead of the component (A) in Example 1. It was.
  • TE-2000 polybutadiene skeleton urethane dimethacrylate
  • Comparative example 4 In Example 1, a preparation was made in the same manner as in Example 1 except that a polyether skeleton urethane diacrylate (UXF-4002, manufactured by Nippon Kayaku Co., Ltd.) was used instead of the component (A). Comparative Example 4 Got.
  • a polyether skeleton urethane diacrylate UXF-4002, manufactured by Nippon Kayaku Co., Ltd.
  • the moisture permeability (g / m 2 ⁇ 24h) was calculated and evaluated based on the following evaluation criteria. The results are shown in Table 2. The detailed test method conforms to JIS Z 0208. It should be noted that the moisture permeability is preferably less than 5 g / m 2 ⁇ 24 h when used as a fuel cell sealant.
  • Moisture permeability is less than 5 g / m 2 ⁇ 24 h
  • Moisture permeability is 5 g / m 2 ⁇ 24 h or more, less than 50 g / m 2 ⁇ 24 h
  • Moisture permeability is 50 g / m 2 ⁇ 24 h or more
  • ⁇ Hydrogen gas barrier test> Using the photocurable sealants for fuel cells of Examples 1 and 2 and Comparative Examples 3 and 4, JIS K7126-1: 2006 (Plastics-Film and Sheet-Gas Permeability Test Method-Part 1: Differential Pressure Method) Measured according to The type of test was the pressure sensor method, the conditions were 23 ° C., the test gas (hydrogen gas) on the high pressure side was measured with a sheet of 100 kPa and a thickness of 1 mm, and evaluated based on the following evaluation criteria. The results are shown in Table 2.
  • the hydrogen gas barrier property is preferably less than 1 ⁇ 10 ⁇ 15 mol ⁇ m / m 2 ⁇ s ⁇ Pa when used as a fuel cell sealant.
  • Comparative Example 3 was a result of using urethane dimethacrylate having a polybutadiene skeleton in place of the component (A), but the result was inferior hydrogen gas barrier properties.
  • Comparative Example 4 the urethane skeleton having a polyether skeleton was used in place of the component (A), but the moisture permeability and hydrogen gas barrier properties were inferior.
  • the photocurable sealant for fuel cells of the present invention is rapidly cured by irradiation with an active energy ray such as an external line, and has excellent adhesion to electrolyte membranes, PP, and PEN, which are difficult-to-adhere materials. It is useful above.
  • a photocurable sealant for a fuel cell comprising the following components (A) to (C): Component (A): Polyisobutylene polymer (B) component having at least one (meth) acryloyl group in the molecule and containing — [CH 2 C (CH 3 ) 2 ] — unit: Photoradical polymerization initiator (C) component : Methacrylate monomer [22]
  • the (C) component methacrylate monomer having an alkyl group having 5 to 30 carbon atoms is heptyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, isooctyl methacrylate, decyl methacrylate, dodecyl methacrylate, isodecyl methacrylate.
  • methacrylate monomer having an alicyclic structure examples include cyclohexyl methacrylate, 4-butylcyclohexyl methacrylate, dicyclopentanyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxy methacrylate, isobornyl methacrylate, and adamantyl methacrylate.
  • the amount of the component (C) is 3 to 300 parts by mass with respect to 100 parts by mass of the component (A), according to any one of the above [21] to [23] Photocurable sealant for fuel cells.
  • R 1 represents a monovalent or polyvalent aromatic hydrocarbon group, or a monovalent or polyvalent aliphatic hydrocarbon group.
  • PIB is a polyisobutylene containing a — [CH 2 C (CH 3 ) 2 ] — unit.
  • R 4 represents a divalent hydrocarbon group which may contain an oxygen atom having 2 to 6 carbon atoms, and R 2 and R 3 are a hydrogen atom and a monovalent hydrocarbon group having 1 to 20 carbon atoms, respectively.
  • R 5 represents a hydrogen atom, a methyl group, an ethyl group or a propyl group, and n is any one of 1 to 6.
  • the photocurable sealant for a fuel cell according to any one of the above [21] to [25] is applied to a flange of a part to be sealed, and irradiated with active energy rays, so that the photocurable resin for a fuel cell is irradiated.
  • a sealing method comprising: curing a sealing agent to form a gasket, and then compressing and sealing with another flange.

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PCT/JP2016/072551 2015-08-18 2016-08-01 燃料電池用光硬化性シール剤、燃料電池およびシール方法 WO2017029978A1 (ja)

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JP2017535320A JP6828230B2 (ja) 2015-08-18 2016-08-01 燃料電池用光硬化性シール剤、燃料電池およびシール方法
US15/752,494 US20180241056A1 (en) 2015-08-18 2016-08-01 Photocurable sealing agent for fuel cell, fuel cell, and sealing method
CA2995835A CA2995835C (en) 2015-08-18 2016-08-01 Photocurable sealing agent for fuel cell, fuel cell, and sealing method
KR1020187005652A KR102604161B1 (ko) 2015-08-18 2016-08-01 연료전지용 광경화성 밀봉제, 연료전지 및 밀봉 방법
CN201680048479.3A CN107925098B (zh) 2015-08-18 2016-08-01 燃料电池用光固化性密封剂、燃料电池和密封方法
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WO2019124252A1 (ja) * 2017-12-18 2019-06-27 株式会社スリーボンド 硬化性樹脂組成物、それを用いた燃料電池およびシール方法
CN110402261A (zh) * 2017-03-16 2019-11-01 株式会社钟化 乙烯基系梳型共聚物
CN110494500A (zh) * 2017-04-14 2019-11-22 三键有限公司 固化性树脂组合物、使用该固化性树脂组合物的燃料电池和密封方法
JPWO2018190144A1 (ja) * 2017-04-10 2020-02-20 株式会社カネカ イソブチレン系重合体の製造方法
JPWO2018190415A1 (ja) * 2017-04-14 2020-03-05 株式会社スリーボンド 光硬化性樹脂組成物、それを用いた燃料電池およびシール方法
JP2021021012A (ja) * 2019-07-29 2021-02-18 アイカ工業株式会社 光硬化型ガスケット樹脂組成物
CN112820986A (zh) * 2019-11-18 2021-05-18 通用汽车环球科技运作有限责任公司 制造具有聚合物保形边缘涂层的袋型电池组电池的方法
WO2021210598A1 (ja) * 2020-04-16 2021-10-21 株式会社スリーボンド 光硬化性組成物、シール剤および硬化物
WO2023002973A1 (ja) * 2021-07-21 2023-01-26 株式会社スリーボンド 光硬化性組成物
WO2023053816A1 (ja) 2021-09-30 2023-04-06 住友理工株式会社 燃料電池用ラジカル硬化性シール部材
JP7335185B2 (ja) 2020-02-28 2023-08-29 アイカ工業株式会社 ハードディスクドライブ用光硬化型ガスケット樹脂組成物及びハードディスクドライブ

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JP7355559B2 (ja) * 2019-08-28 2023-10-03 住友理工株式会社 燃料電池用ラジカル硬化性シール部材
CN110605777B (zh) * 2019-09-17 2024-04-30 苏州可川电子科技股份有限公司 一种解决3d立体云母表面贴胶的工艺
CN114149678B (zh) * 2022-01-10 2023-10-10 南亚新材料科技股份有限公司 热固性树脂组合物、增强材料、覆金属层压板及其应用

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WO2018003855A1 (ja) * 2016-06-28 2018-01-04 株式会社スリーボンド 硬化性樹脂組成物、燃料電池およびシール方法
US10907037B2 (en) 2016-06-28 2021-02-02 Threebond Co., Ltd. Curable resin composition, fuel cell, and sealing method
EP3597681A4 (en) * 2017-03-16 2021-01-13 Kaneka Corporation VINYL-BASED AND COMB-TYPE COPOLYMER
JP7069117B2 (ja) 2017-03-16 2022-05-17 株式会社カネカ ビニル系櫛型共重合体
CN110402261A (zh) * 2017-03-16 2019-11-01 株式会社钟化 乙烯基系梳型共聚物
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JPWO2018190144A1 (ja) * 2017-04-10 2020-02-20 株式会社カネカ イソブチレン系重合体の製造方法
JP7022115B2 (ja) 2017-04-10 2022-02-17 株式会社カネカ イソブチレン系重合体の製造方法
JP7149479B2 (ja) 2017-04-14 2022-10-07 株式会社スリーボンド 光硬化性樹脂組成物、それを用いた燃料電池およびシール方法
CN110494500A (zh) * 2017-04-14 2019-11-22 三键有限公司 固化性树脂组合物、使用该固化性树脂组合物的燃料电池和密封方法
US11114679B2 (en) 2017-04-14 2021-09-07 Threebond Co., Ltd. Curable resin composition, and fuel cell and sealing method using the same
CN110494500B (zh) * 2017-04-14 2022-02-08 三键有限公司 固化性树脂组合物、使用该固化性树脂组合物的燃料电池和密封方法
JPWO2018190415A1 (ja) * 2017-04-14 2020-03-05 株式会社スリーボンド 光硬化性樹脂組成物、それを用いた燃料電池およびシール方法
WO2019124252A1 (ja) * 2017-12-18 2019-06-27 株式会社スリーボンド 硬化性樹脂組成物、それを用いた燃料電池およびシール方法
JP2021021012A (ja) * 2019-07-29 2021-02-18 アイカ工業株式会社 光硬化型ガスケット樹脂組成物
CN112820986A (zh) * 2019-11-18 2021-05-18 通用汽车环球科技运作有限责任公司 制造具有聚合物保形边缘涂层的袋型电池组电池的方法
JP7335185B2 (ja) 2020-02-28 2023-08-29 アイカ工業株式会社 ハードディスクドライブ用光硬化型ガスケット樹脂組成物及びハードディスクドライブ
WO2021210598A1 (ja) * 2020-04-16 2021-10-21 株式会社スリーボンド 光硬化性組成物、シール剤および硬化物
WO2023002973A1 (ja) * 2021-07-21 2023-01-26 株式会社スリーボンド 光硬化性組成物
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CA2995835A1 (en) 2017-02-23
KR102604161B1 (ko) 2023-11-20
JP6828230B2 (ja) 2021-02-10
KR20180041680A (ko) 2018-04-24
EP3340352A4 (en) 2019-03-20
US20180241056A1 (en) 2018-08-23
CA2995835C (en) 2023-09-26
CN107925098B (zh) 2021-07-09
EP3340352A1 (en) 2018-06-27
CN107925098A (zh) 2018-04-17
JPWO2017029978A1 (ja) 2018-08-02

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